Fertilizers and process for their production



Patented Apr. 7, 1936 wee-D STATES PATENT OFFICE FERTILIZERS AND PROCESS FOR THEIR PRODUCTION Edward W. Harvey, New Brunswick, N. J., as-

signor to The Barrett Company, New York, N. Y., a corporation of New Jersey No Drawing. Application September 15, 1932,

Serial No. 633,270

12 Claims.

phosphate, double superphosphate and mixtures containing one or both of the same are examples of monocalcium acid phosphate materials.

superphosphate, for example, is frequently a constituent of fertilizer mixtures. This material supplies the P205 which is desirable as a plant food. Nitrogen is also a desirable plant food in fertilizers and, in order to prepare materials containing both P205 and nitrogen, it has heretofore been proposed to absorb ammonia in superphosphate. A difiiculty with such a method of preparation of a fertilizer arises from the fact that when relatively large amounts of ammonia-are added to a superphosphate it causes available P205 (water soluble and citrate soluble P205) to revert to a citrate insoluble form which is not considered available as a plant food. There is, therefore, a limitation in the amount of. nitrogen which may practically be added to superphosphate by meansof treating it withammonia. Urea is a highly concentrated nitrogen-containing materiaL' It has alsobeen proposed to introduce urea into fertilizers containing a superphosphate but the difficulties encountered with the fertilizers 1 thus produced are that they are hygroscopic, become sticky and are not satisfactory with respect to their physical character.

It is an object of this invention to'pro-vide. a

fertilizer containing a superphosphate and nitro-.

gen, in which the nitrogen may be present in relatively large amounts, which retains a dry- -to-thetouch free-flowing character when exposed to an atmosphere containing the humidities usually encountered, for long periods of time. It is a fur.- ther object of this inventionto prepare a mixed fertilizer containing urea in which the urea is substantially uniformly distributed throughout with ammonia, preferably in the form of aqua ammonia. The ammonia may also be advantageously employed in the form of liquid anhydrous ammonia, particularly when triple superphosphate is a constituent of the fertilizer mix- 5 ture. The fertilizer may conveniently be prepared by simultaneously mixing the ammonia, urea and superphosphate material or, if desired, the solid materials may first be mixed in the usual mixing machines used in fertilizer practice 10 and the ammonia may then rapidly be introduced 7 into the mixer and disseminated throughout the mass of solid material by continuing the mixing operation during and for a short time after the k introduction of the ammonia. l5 This invention may likewise be utilized in the production of fertilizers by introducing a solution of urea in aqua or anhydrous liquid ammonia into a mixer in which superphosphate is being agitated or in which superphosphate is being ad- 20 mixed with other desirable constituents of a complete fertilizer such as potassium salts, fillers and the like. It is particularly advantageous to employ the ammonia in suficient amount to re- .act with substantially all of the water soluble 25 phosphates in the superphosphate (free phosphoric acid or monocalcium acid phosphate) to form di-ammonium phosphate. This di-ammonium phosphate may, however, react with other constituents of the materials and, in the 30 caseof treating superphosphate, it appears in fact to react with the calcium sulfate which is present in superphosphate so that the ammonia added eventually is converted into ammonium sulfate with the formation of water insoluble 35 dicalcium phosphate which, however, is citrate soluble and hence available to plants.

The following examples are illustrative of f processes for the production of fertilizers in accordance with my invention but the scope of the 40 invention is not limited to the exact details set forth.

' Example I The following materials are introduced into a mixing machine and thoroughly intermixed with one another:

\ 7 Parts- Superphosphate 47 Urea I 8 50 Potassium su1fate 14 Filler (sand) 25 To the mixed materials about 6 parts of 25% aqua ammonia are added while the mixing is continued to thoroughly disseminate the am- Example V v Parts Superphosphat 4'7 Sulfate of ammonia 6 Potassium chloride 14 Urea 4 Filler 24 treated with about "2 parts of anhydrous liquid 7 ammonia.

Example VI Parts Superphosphat 47 Sulfate of ammonia- 10 I Potassium ide 14 Filler (sand) 26 monia throughout. the solid material. The ammonia liquor may be introduced in the form of a spray applied to the solids undergoing agitation.

and the mixture treated with about 6 parts of ammonia liquor containing 25% N113.

Fertilizers may be prepared in accordance with this invention by mixing the solid ingredients of the following examples and treating the mixture with the ammoniacal liquid given in each example, preferably by spraying the liquid on the mixture of solids while it is being agitated. 'Instead of first mixing the solid materials, they may be-simultaneously treated with the ammoniacal liquid while being admixed or the superphosphate may be treated with the ammoniacal liquid and the. resulting material admixed with the remaining constituents of the examples.

Example III Parts Superphosphate 4'7 Sulfate of ammonia 8 Potassium chloride 14 Urea 4 Filler 21 treated with about 6 parts of aqua ammonia containing 25% NH:;.

treated with about4 parts of aqua ammonia containing 50% NHa.

treated with about 3 parts of a solution of urea in anhydrous liquid ammonia containing about 1 part of urea for every 2' parts of ammonia.

Example VII i Parts Superphosphat 47 Sulfate of ammonia 8 Potassium chloride 14 Filler (sand) 25.

treated with about 6 parts ofa solution of urea, ammonia and water containing about equal proportions of the three constituents of the solution.

Example VIII Parts Superphosnhate 4 47 Potassium chloride 14 Urea 2 Sodium nitra 5 Filler 30 treated with about 2 parts of liquid anhydrous ammonia.

Example IX I Parts Superphosphate 4'7 Potassium chloride- L 14 Urea g. 2 Sodium nitrate 5 Ammonium sulfate 4 Filler 26 sist or sand or a filler may be employed which contains, in addition to or in place of sand, peat,

peanut meal, cocoa shell meal, garbage tankage, etc. Organic materials such as cottonseed meal, fish scrap, tankage, blood, etc., may also be employed in preparing fertilizer mixtures in accordance with the process of this invention.

In preparing a fertilizer in accordance with this invention it is preferred to employ the ammonia in su flicient amount to react with the freephosphoric acid and the monocalcium phosphate in the superphosphate or triple superphosphate to form di-ammonium phosphate. Urea is a basic substance and has the property of combining with acidic materials. By employing sufllcient ammonia to react with the acidic constituents of the superphosphates a combination of urea and these constituents appears to be prevented or, if the urea is first'mixed with the superphosphate and the ammonia subsequently added, the ammonia acting as a stronger base than the urea may displace the urea from its combination. In either mode of operation, 1. e., whether the urea be first added to the superphosphate and then the ammonia introduced, or whether the ammonia be added simultaneously with or prior to the addition of the urea, the

urea in the resulting product appears to be in a free condition and this is believed to be an important factor in obtaining a product which is non-hygroscopic, retains a granular condition for long periods of time and is stable with respect to its nitrogen content. It should be noted that by the addition of urea itself to superphosphate the acid character of the superphosphate may be destroyed in a greater or less degree depending upon the amount of urea used. In carrying out the process of this invention, therefore,

in the modification just described, where the amount of ammonia is sufncient to form diammonium phosphate with the acidic phosphate constituents, the ammonia is added inamount greater than would be necessary to merely neutralize the free acidity oi. the superphosphate left after the'addltion of the urea...

instead of employing the ammonia in amount suflicient to form di-ammonium phosphate I have found a smaller amount of ammonia may be used and a product of the desired character may be obtained by utilizing an ammoniacal' liquid, for example, aqua ammonia or liquid anhydrous ammonia, in the treatment of mixtures of urea and superphosphate or by adding the urea to the superphosphate in solution in these ammoniacal liquids. Since in compounding mixed fertilizers relatively small amounts of urea are employed as compared with the amount of superphosphate and other solid material with which it is to be admixed, it has been found particularly difficult to obtain a satisfactorily uniform distribution of the urea. By introducing the urea as a solution of it in liquid anhydrous ammonia or in aqua ammonia its distribution throughout the mass of material is greatly facilitated, The relatively" high solubility of the urea in aqua ainmonia or anhydrous liquid ammonia also permits of securing a sufficiently uniform distribution of the urea by treating a mixture of the solid components of the fertilizer including solid finely divided urea with the ammoniacal liquid.

Urea itself is hygroscopic, although it is less hygroscopic than its reaction products with superphosphate materials when ammonia is not also present. It is particularly desirable, therefore, to obtain uniform distribution of the urea since, if it is segregated to any considerable degree in portions of the mixed fertilizer, it will tend to form wetspots in the fertilizer, which make it undesirable for distribution to the trade. By distributing the urea to the mixture employing an ammoniacal liquid as a vehicle for this distribution, not only will the urea be well distributed throughout the mass but, as the ammonia reacts with the acidic constituents of the mixture, ammonium salts will be formed which will deposit in admixture with the urea and thus improve the quality of the product.

It is also possible to employ the process of this invention to advantage in the preparation of fertilizers containing urease constituents by employing the ammonia in the form either of, for example, liquid anhydrous ammonia or of a relatively concentrated aqua ammonia containing, for example, 50% NH3. By employing these concentrated ammoniacal liquids the heat evolved in the reaction of the ammonia with the phosphate material is suflicient to heat the mixed materials to a temperature sufficiently high to destroy the urease which may be present without attaining, however, a high enough temperature to materially deleteriously affect the availability of the P205 in the ammoniated material.

Numerous modifications and changes may be made in the processes described above without departing from. the scope of this invention. Fertilizers prepared in accordance with my invention may contain any of the usual constituents of mixed fertilizers such as potassium salts (potassium chloride, potassium sulfate, potassium nitrate), ammonium sulfate, sodium nitrate, calcium nitrate, ammonium phosphate. These materials together with the urea may be added to the superphosphate and mixed therewith in the dry state and the mixture then treated with the ammonia, or the urea may be added in solution in an ammoniacal liquid to the remaining solid constituents of the mixture either after the solids have been admixed or simultaneously with g in the form of a solution in the urea-ammonia liquid.

The fertilizers of the examples given above,

comprising ammoniated superphosphate and the indicated soluble fertilizer salts, such as ammonium sulfate, potassium chloride, sodium nitrate and urea, are all of high value since they contain the three fertilizer ingredients phosphorous, nitrogen and potassium. The fer tilizers of Examples VIII and IX are particularly of value with respect to their nitrogen content since they contain the nitrogen in the three forms of ammoniacal nitrogen, nitrate nitrogen and amide nitrogen. The nitrate nitrogen is especially desirable because of its quick action and promotes rapid early growth of the plants. The nitrogen in the form of ammonia is somewhat slower acting and is in a form in which it is not quickly leached out of the soil, while the nitrogen in the form of urea, is somewhat more lasting even than the ammonium nitrogen and is in the form of an organic compound which is considered highly desirable.

I claim:

1. The process of producing a fertilizer which comprises treating a material containing mono- ,calcium acid phosphate with an ammoniacal socomprises mixing a solution of urea in aqua ammonia with. a material containing superphosphate. 1

5. A superphosphate nitrifying agent comprising a liquid containing dissolved free ammonia and urea.

6. Process for the production of a fertilizer which, comprises incorporating a solution of urea and free ammonia with a superphosphate.

7. A superphosphate nitrifying agent comprising a liquid containing in solution free ammonia, urea, and water.

8. A process. for the production of fertilizer which comprises incorporating with a super- 7 with a solution of urea and free ammonia containing about 1 to 2 parts of ammonia for every 1 part of urea. S

12. A superphosphate nitrifying agent comprising a solution of urea in anhydrous liquid ammonia.

EDWARD W. HARVEY. 

